CN102812101B - Thermally expandable microcapsule - Google Patents
Thermally expandable microcapsule Download PDFInfo
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- CN102812101B CN102812101B CN201180015090.6A CN201180015090A CN102812101B CN 102812101 B CN102812101 B CN 102812101B CN 201180015090 A CN201180015090 A CN 201180015090A CN 102812101 B CN102812101 B CN 102812101B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
- B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/66—Anhydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
Disclosed is a thermally expandable microcapsule, which causes less bursting or shrinking even at a high temperature while maintaining a high expansion ratio. Also disclosed are an expandable thermoplastic resin masterbatch using the thermally expandable microcapsule, an expansion-molded article, and a method for producing the thermally expandable microcapsule. The thermally expandable microcapsule comprises a shell composed of a polymer and a volatile expanding agent as a core agent encapsulated in the shell. The shell contains a polymer obtained by polymerizing a monomer composition containing a nitrile-based monomer and a monomer having a carboxyl group and a thermosetting resin. The thermosetting resin has two or more functional groups which react with a carboxyl group in each molecule and does not have a radically polymerizable double bond.
Description
Technical field
The present invention relates to maintain high foamability and be at high temperature difficult to produce break or the manufacture method of the thermal expansivity micro-capsule shrinking, the foaminess thermoplastic resin masterbatch that uses this thermal expansivity micro-capsule and this thermal expansivity micro-capsule.
Background technology
Thermal expansivity micro-capsule is being used in purposes widely as appearance design imparting agent and light weight agent, is also used in that to take foam ink, wallpaper be the main coating that turns to object with light weight etc.
As such thermal expansivity micro-capsule, extensively the temperature below the known softening temperature that wraps in shell polymeric in having in thermoplastic shell polymkeric substance is issued to the micro-capsule of gasiform volatile expanding agent, for example, following method is disclosed in patent documentation 1: when stirring in the oiliness mixed solution that the volatile expanding agents such as lower boiling aliphatic hydrocarbon are mixed with monomer, the water system dispersion medium that is containing dispersion agent together with oil soluble polymerizing catalyst, add, carry out suspendible polymerization, thus, manufacture the thermal expansivity micro-capsule of interior bag volatile expanding agent.
But, the thermal expansivity micro-capsule obtaining by the method, at the lower temperature of approximately 80～130 ℃, although can make by the gasification of volatile expanding agent its thermal expansion, but when high temperature or long-time heating, withdrawing gas from the micro-capsule expanding, thus, the problem that exists expansion ratio to reduce.In addition, due to the thermotolerance of thermal expansivity micro-capsule and the problem of intensity, produce so-called being called as the phenomenon of " permanent strain (ヘ り) ", sometimes when high temperature, collapse.
On the other hand, a kind of thermal expansivity micro-capsule is disclosed in patent documentation 2, use the monomer that contains carboxyl and have that monomer with the group of carboxyl reaction carries out polymerization and the polymkeric substance that obtains as shell.In such thermal expansivity micro-capsule, by improving three-dimensional cross-linked density, even under the very thin state of the shell after foaming, for shrinking, also demonstrate strong resistance, thermotolerance improves fast.
But, in polymerization, constantly form strong three-dimensional cross-linked, thus, the expansion while hindering foaming, about expansion ratio, still insufficient.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 42-26524 communique
Patent documentation 2: International Publication WO99/43758 brochure
Summary of the invention
Invent problem to be solved
The object of the invention is to, the manufacture method that maintains the foaminess thermoplastic resin masterbatch, foam molding and this thermal expansivity micro-capsule that are difficult to produce the thermal expansivity micro-capsule that breaks and shrink under high foamability and high temperature, use this thermal expansivity micro-capsule is provided.
The means of dealing with problems
The present invention is a kind of thermal expansivity micro-capsule, it for being wrapped in the shell consisting of polymkeric substance in the volatile expanding agent as core agent, described shell contains: polymkeric substance and thermosetting resin that the monomer composition of the monomer that contains nitrile monomer and have carboxyl is polymerized, described thermosetting resin has more than 2 the functional group with carboxyl reaction in 1 molecule, and does not have free-radical polymerised two keys.
Below, describe the present invention in detail.
The inventor finds, in thermal expansivity micro-capsule, the shell of the thermosetting resin that contains polymkeric substance that the monomer composition of the monomer that contains nitrile monomer and have carboxyl is polymerized, regulation by use, can maintain high foamability, and breaking and shrinking under inhibition high temperature, thereby completed the present invention.
Thermal expansivity micro-capsule of the present invention, have in the shell being formed by polymkeric substance in bag as the structure of the volatile expanding agent of core agent.By thering is such structure, for example, thermal expansivity micro-capsule of the present invention is coordinated and is shaped in matrix resin, thus, utilize the heating while being shaped, above-mentioned core agent forms gas shape, and simultaneously above-mentioned shell occurs softening and expands, and can manufacture foam molding etc.
The monomer composition that is used to form above-mentioned polymkeric substance, contains nitrile monomer.By above-mentioned monomer composition, contain above-mentioned nitrile monomer, resulting thermal expansivity micro-capsule has high heat resistance and barrier properties for gases.
Above-mentioned nitrile monomer is not particularly limited, and for example, can enumerate: vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, α-ethoxy propylene nitrile, flumaronitrile or these mixture etc.In these, be particularly preferably vinyl cyanide and methacrylonitrile.These can use separately, also can be used together more than two kinds.
The content of the above-mentioned nitrile monomer in above-mentioned monomer composition, preferred lower limit, is 50 weight parts with respect to whole monomer component 100 weight parts, is limited to 99 weight parts on preferred.When the content of above-mentioned nitrile monomer is less than 50 weight part, barrier properties for gases reduces, thus, sometimes expansion ratio reduces, and while surpassing 99 weight part, the content of carboxyl becomes insufficient, when foamable, be combined with thermosetting resin, thus, resulting effect becomes insufficient sometimes.
Under preferred, be limited to 60 weight parts, be limited to 95 weight parts on preferred.
Above-mentioned monomer composition, except above-mentioned nitrile monomer, also contains the above-mentioned monomer with carboxyl.
By containing the above-mentioned monomer with carboxyl, resulting thermal expansivity micro-capsule, the heat while utilizing foamable, carboxyl is combined with thermosetting resin, therefore, can make thermotolerance and weather resistance further improve.
As the above-mentioned monomer with carboxyl, for example, can enumerate: the unsaturated dicarboxylic acids such as the unsaturated monocarboxylics such as vinylformic acid, methacrylic acid, ethylacrylic acid, β-crotonic acid, styracin, toxilic acid, methylene-succinic acid, fumaric acid, citraconic acid etc.In addition, also can use their salt or acid anhydrides.In these, be preferably vinylformic acid, methacrylic acid.
The above-mentioned content with the monomer of carboxyl in above-mentioned monomer composition, preferred lower limit is 1 weight part, is limited to 50 weight parts on preferred with respect to whole monomer component 100 weight parts.When the above-mentioned content with the monomer of carboxyl is less than 1 weight part, by being combined with thermosetting resin when the foamable, resulting effect becomes insufficient sometimes, while surpassing 50 weight part, hinders the barrier properties for gases of shell, and expansion ratio reduces sometimes.
Under preferred, be limited to 5 weight parts, be limited to 40 weight parts on preferred.
Above-mentioned monomer composition, except above-mentioned nitrile monomer, have the monomer of carboxyl, can also contain can with other monomers (following, to be also simply called other monomers) of above-mentioned nitrile monomer copolymerization.
Above-mentioned other monomers are not particularly limited, and can, according to the necessary characteristic of resulting thermal expansivity micro-capsule is suitably selected, for example, can enumerate: Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, molecular weight is two (methyl) acrylate of 200～600 polyoxyethylene glycol, glycerine two (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, oxyethane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, triallyl formal three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, dihydroxymethyl-tristane two (methyl) acrylate etc.In addition, as above-mentioned other monomers, for example, also can enumerate: the vinyl monomers such as methyl acrylic ester, vinylchlorid, vinylidene chloride, vinyl-acetic ester, vinylbenzene such as the esters of acrylic acids such as methyl acrylate, ethyl propenoate, butyl acrylate, dicyclopentenyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, isobornyl methacrylic ester etc.These can use separately, also can be used together more than two kinds.
In the situation that above-mentioned monomer composition contains above-mentioned other monomers, the content of above-mentioned other monomers in above-mentioned monomer composition is not particularly limited, and with respect on whole monomer component 100 weight parts preferred, is limited to 40 weight parts.When the content of above-mentioned other monomers surpasses 40 weight part, the content of above-mentioned nitrile monomer reduces, and the thermotolerance of resulting thermal expansivity micro-capsule and barrier properties for gases reduce, and under high temperature, easily produces and breaks and shrink, and sometimes cannot foam with high foamability.
Can in above-mentioned monomer composition, add metallic cation salt.
By adding above-mentioned metallic cation, for example, the carboxyl of above-mentioned carboxylic monomer and above-mentioned metallic cation form ionomer, the cross-linking efficiency of the shell of resulting thermal expansivity micro-capsule improves, thermotolerance improves, even if be at high temperature also difficult to produce, break and shrink, can foam with high foamability.In addition, by forming above-mentioned ionomer, the resulting thermal expansivity micro-capsule at high temperature Young's modulus of shell is also difficult to reduce.Therefore, after such thermal expansivity micro-capsule coordinates in matrix resin, by applying in the situation that the manufacturing process such as mixing shaping, calendaring molding (カ レ Application ダ mono-is shaped), extrusion molding, injection forming of strong shearing force are shaped, also be difficult to generate and break and shrink, can foam with high foamability.
Form the metallic cation of above-mentioned metallic cation salt, for example, so long as can form with the carboxyl of the carboxylic monomer such as methacrylic acid the metallic cation of ionomer, be not particularly limited, for example, can enumerate: the ion of Na, K, Li, Zn, Mg, Ca, Ba, Sr, Mn, Al, Ti, Ru, Fe, Ni, Cu, Cs, Sn, Cr, Pb etc.In these, preferably as Ca, Zn, the ion of Al, the particularly preferably ion of Zn of the metallic cation of 2～3 valencys.
In addition, above-mentioned metallic cation salt, is preferably the oxyhydroxide of above-mentioned metallic cation.These can use separately, also can be used together more than two kinds.
By above-mentioned metallic cation salt and with more than two kinds in the situation that, for example, the salt that preferably combination use consists of the ion of basic metal or alkaline-earth metal, the salt being formed by above-mentioned basic metal or alkaline-earth metal metallic cation in addition.The ion of above-mentioned basic metal or alkaline-earth metal, can make functional group's sensitizations such as carboxyl, can promote the ionomer of the functional groups such as this carboxyl and above-mentioned basic metal or alkaline-earth metal metallic cation in addition to form.
Above-mentioned basic metal or alkaline-earth metal are not particularly limited, and for example, can enumerate: Na, K, Li, Ca, Ba, Sr etc.In these, be preferably Na, K etc. that alkalescence is strong.
The content of the above-mentioned metallic cation salt in above-mentioned monomer composition is not particularly limited, with respect to being limited to 0.01 weight part under whole monomer component 100 weight parts preferred, being limited to 10 weight parts on preferred.When the content of above-mentioned metallic cation salt is less than 0.01 weight part, the stable on heating effect of the resulting thermal expansivity micro-capsule that sometimes cannot be improved fully.When the content of above-mentioned metallic cation salt surpasses 10 weight part, resulting thermal expansivity micro-capsule can not foam with high foamability sometimes.
Preferably in above-mentioned monomer composition, add polymerization starter.
Above-mentioned polymerization starter is not particularly limited, and for example, can enumerate: dialkyl, peroxidation diacyl, peroxyester, peroxy dicarbonate, azo-compound etc.
Above-mentioned dialkyl is not particularly limited, and for example, can enumerate: methylethyl superoxide, ditertiary butyl peroxide, dicumyl peroxide, isobutyl peroxide etc.
Above-mentioned peroxidation diacyl is not particularly limited, and for example, can enumerate: benzoyl peroxide, 2,4 dichlorobenzoyl peroxide, 3,5,5-trimethyl acetyl base superoxide etc.
Above-mentioned peroxyester is not particularly limited, for example, can enumerate: t-butylperoxy pivarate, tertiary hexyl peroxidation pivalate, tert-butyl hydroperoxide neodecanoic acid ester, tertiary hexyl new decanoate ester peroxide, 1-cyclohexyl-1-methylethyl new decanoate ester peroxide, 1,1,3,3-tetramethyl butyl new decanoate ester peroxide, cumyl new decanoate ester peroxide, (α, the peroxidation of α-bis--Xin caprinoyl) diisopropyl benzene etc.
Above-mentioned peroxy dicarbonate is not particularly limited, for example, can enumerate: two (4-tert-butylcyclohexyl) peroxy dicarbonate, two-n-propyl-peroxy dicarbonate, diisopropyl peroxydicarbonate, two (peroxidation of 2-ethyl diethyldithiocarbamate) two carbonic ethers, dimethoxy butyl peroxyization two carbonic ethers, two (3-methyl-3-methoxyl group butyl peroxy) two carbonic ethers etc.
Above-mentioned azo-compound is not particularly limited, and for example, can enumerate: 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 1,1 '-azo two (1-cyclohexane nitrile) etc.
As required, in above-mentioned monomer composition, can also add stablizer, UV light absorber, antioxidant, antistatic agent, fire retardant, silane coupling agent, toner etc.
The weight-average molecular weight of the polymkeric substance that makes monomer composition polymerization as above and obtain is not particularly limited, and is limited to 100,000 under preferred, is limited to 2,000,000 on preferred.Above-mentioned weight-average molecular weight is less than at 100,000 o'clock, and the strength decreased of the shell of resulting thermal expansivity micro-capsule easily produces and breaks and shrink under high temperature, sometimes cannot foam with high foamability.Above-mentioned weight-average molecular weight surpasses at 2,000,000 o'clock, and the intensity of the shell of resulting thermal expansivity micro-capsule is too high, and foam performance reduces sometimes.
The shell that forms thermal expansivity micro-capsule of the present invention contains thermosetting resin.
Above-mentioned thermosetting resin, occurs to solidify owing to not being foamable when the polymerization of above-mentioned monomer composition but at thermal expansivity micro-capsule, therefore, in the situation that the expansion while not hindering foaming can improve expansion ratio.
As above-mentioned thermosetting resin, for example, can enumerate: epoxy resin, resol, melamine resin, urea resin, polyimide resin, bimaleimide resin etc.In these, be preferably epoxy resin, resol.
As above-mentioned epoxy resin, be not particularly limited, for example, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, dicyclopentadiene-type epoxy resin, glycidyl group amine type epoxy resin etc.
As above-mentioned resol, for example, can enumerate: phenolic varnish type resol, first rank novolac type phenolic resin, benzylic ether type resol etc.In these, be preferably phenolic varnish type resol.
Above-mentioned thermosetting resin does not have free-radical polymerised two keys.
By not having above-mentioned free-radical polymerised two keys, the main chain Direct Bonding of the polymkeric substance that can not be polymerized with the monomer composition that makes to contain above-mentioned nitrile monomer and have the monomer of carboxyl, can keep compared with highland the flexibility of shell.
For example, in method in the past (, patent documentation 2 etc.), have the monomer of free-radical polymerised two keys by use, the barrier properties for gases of shell reduces, and expansion ratio reduces.
In addition, above-mentioned thermosetting resin has more than 2 and functional group carboxyl reaction in 1 molecule.By thering is the functional group of 2 above above-mentioned and carboxyl reactions, can make the solidified nature of thermosetting resin more strong.Particularly in the situation that above-mentioned monomer composition comprises the monomer with carboxyl, the heat while utilizing foamable, carboxyl and the combination of more strong ground of thermosetting resin, thus can make thermotolerance and weather resistance significantly improve.
As above-mentioned and functional group carboxyl reaction, for example, can enumerate: epoxy group(ing), phenylol, methylol, amino etc.Wherein, be preferably epoxy group(ing).As above-mentioned and functional group carboxyl reaction, can use the functional group of identical type, also can use two kinds of above functional groups.
As not thering are above-mentioned free-radical polymerised two keys, and in 1 molecule, there is thermosetting resin more than 2 and functional group carboxyl reaction, for example, can enumerate: epoxy resin, resol, urea resin, melamine resin, Sorbitol Powder poly epihydric alcohol base ether (デ Na コ mono-Le EX-622), Polyglycerine poly epihydric alcohol base ether (デ Na one Le EX-521), two glycerine poly epihydric alcohol base ethers (デ Na one Le EX-421), glycerine poly epihydric alcohol base ether (デ Na one Le EX-313), tetramethylolmethane poly epihydric alcohol base ether (デ Na コ mono-Le EX-411), Resorcinol diglycidyl ether (デ Na コ mono-Le EX-201), 1, 6-hexylene glycol diglycidyl ether (デ Na コ mono-Le EX-212), ethene, polyoxyethylene glycol diglycidyl ether (more than, Na ガ セ ケ ムテツク ス company system, デ Na コ mono-Le EX-810) etc.
The solidification value of above-mentioned thermosetting resin is preferably more than 120 ℃.
By making the solidification value of above-mentioned thermosetting resin, be more than 120 ℃, during the polymerization of the polymkeric substance being polymerized due to the monomer composition making to contain above-mentioned nitrile monomer, do not solidify, therefore the expansion in the time of can not hindering foamable, can improve expansion ratio.
It should be noted that, above-mentioned solidification value, gelling temperature when can the mixture of thermosetting resin and citric acid be heated by mensuration is obtained.
Above-mentioned thermosetting resin は, the Temperature Setting when the vapour pressure of core agent is reached to 1.0MPa are T1.0, when the Temperature Setting when vapour pressure of above-mentioned core agent is reached to 1.5MPa is T1.5, preferably the gel percentage under T1.0 is less than 5%, and the gel percentage under T1.5 is more than 5%.
It should be noted that, the vapour pressure of above-mentioned core agent can calculate by Antoine equation.
Gel percentage about above-mentioned thermosetting resin, with gelating agent, make after thermosetting resin swelling, can by calculate swelling body dry weight, measure with the weight ratio [swelling body dry weight/(weight of the weight+gelating agent of thermosetting resin)] of the gross weight of thermosetting resin and gelating agent.
It should be noted that above-mentioned gelating agent, according to the kind of thermosetting resin, can be used the material of regulation.
T1.0 is speculated as and approaches the temperature that thermal expansivity micro-capsule starts foaming.
Therefore, the gel percentage under the T1.0 of above-mentioned thermosetting resin is 5% when above, and thermosetting resin over-curing when foaming starts, therefore, hinders foaming sometimes.In addition, thereupon, the Dmax of the particle after foaming (maximum foaming displacement) reduces sometimes.In addition, the expansion ratio of foam molding reduces.
T1.5 is that the interior pressure as core agent improves, likely occurs the broken bubble of thermal expansivity micro-capsule or degassed temperature.
Therefore,, when the gel percentage under the T1.5 of above-mentioned thermosetting resin is less than 5%, in the moment that reaches this temperature, if do not carry out solidifying of thermosetting resin, sometimes cause breaking or permanent strain of shell.In addition, thereupon, the Δ T (weather resistance) of the thermal expansivity micro-capsule after foaming reduces sometimes.In addition, in foam molding, sometimes easily produce broken bubble.
As the gel percentage meeting under the T1.0 of above-mentioned thermosetting resin, be less than 5%, and the gel percentage under T1.5 is more than 5% condition, the combination of thermosetting resin and core agent, for example, can enumerate: the エ ピ コ mono-ト 828US (japan epoxy resin company system) that is used as thermosetting resin, iso-pentane (30 % by weight) as core agent: the combination of the mixture of octane-iso (70 % by weight), or be used as the jER630 (japan epoxy resin company system) of thermosetting resin, iso-pentane (70 % by weight) as core agent: the combination of the mixture of octane-iso (30 % by weight) etc.
The preferred lower limit of the content of the thermosetting resin in above-mentioned shell, is 0.01 % by weight, is limited to 30 % by weight on preferred with respect to the polyalcohol integral that forms shell.
When the content of above-mentioned thermosetting resin is less than 0.01 % by weight, sometimes when foamable, do not demonstrate thermofixation characteristic.When the content of above-mentioned thermosetting resin surpasses 30 % by weight, the barrier properties for gases of shell reduces, and sometimes hinders foaming.Under preferred, be limited to 0.1 % by weight, be limited to 15 % by weight on preferred.It should be noted that, the polyalcohol integral of above-mentioned formation shell refers to the polyalcohol integral of the formation shell except thermosetting resin.
In addition, above-mentioned thermosetting resin and the above-mentioned ratio with the monomer of carboxyl, be preferably 1 times above (carboxylic monomer/thermosetting resin >=1).By being set in above-mentioned scope, can reduce the non-reacted parts of thermosetting resin, performance solidified nature.
In thermal expansivity micro-capsule of the present invention, bag is as the volatile expanding agent of core agent.
In this specification sheets, volatile expanding agent refers to and at the temperature below the softening temperature of above-mentioned shell, forms gasiform material.
As above-mentioned volatile expanding agent, for example, can enumerate: low molecular weight hydrocarbon, the CCl such as ethane, ethene, propane, propylene, normal butane, Trimethylmethane, butylene, iso-butylene, Skellysolve A, iso-pentane, neopentane, normal hexane, heptane, sherwood oil
3f, CCl
2f
2, CClF
3, CClF
2-CClF
2in tetraalkyl silane such as cfc, tetramethylsilane, trimethylammonium ethylsilane, trimethyl isopropyl silane, trimethylammonium-n-propyl silane etc.Wherein, be preferably Trimethylmethane, normal butane, Skellysolve A, iso-pentane, normal hexane, sherwood oil and their mixture.These volatile expanding agents can be used separately, also can be used together more than two kinds.
In thermal expansivity micro-capsule of the present invention, in above-mentioned volatile expanding agent, preferably using carbonatoms is the low boiling hydrocarbon below 10.By using such hydrocarbon, can access the thermal expansivity micro-capsule that expansion ratio is high, start rapidly foaming.
In addition, as volatile expanding agent, can use by heating thermolysis occurs, to reach gasiform thermolysis type compound.
In thermal expansivity micro-capsule of the present invention, under the content of the volatile expanding agent using as core agent preferred, be limited to 10 % by weight, be limited to 25 % by weight on preferred.
The thickness of above-mentioned shell changes according to the content of core agent, but reduces the content of core agent, and when shell becomes blocked up, foam performance reduces, while increasing the content of core agent, and the strength decreased of shell.In the situation that make the content of above-mentioned core agent, be 10～25 % by weight, the permanent strain that can simultaneously realize thermal expansivity micro-capsule prevents from improving with foam performance.
The maximum blowing temperature (Tmax) of thermal expansivity micro-capsule of the present invention is not particularly limited, and is limited to 200 ℃ under preferred.When above-mentioned maximum blowing temperature is less than 200 ℃, the thermotolerance of thermal expansivity micro-capsule reduces, and under high temperature, easily produces and breaks and shrink, and sometimes cannot foam with high foamability.In addition, when above-mentioned maximum blowing temperature is less than 200 ℃, for example, in the situation that using thermal expansivity micro-capsule to manufacture masterbatch pellet, the shearing force during by granule manufacture produces foaming, sometimes can not stably manufacture the not masterbatch pellet of foaming.The maximum blowing temperature of above-mentioned thermal expansivity micro-capsule, is limited to 210 ℃ under preferred.
It should be noted that, in this specification sheets, above-mentioned maximum blowing temperature refers to, when thermal expansivity micro-capsule is measured to its diameter when normal temperature starts heating, the temperature of thermal expansivity micro-capsule while reaching maximum displacement.
The foaming of thermal expansivity micro-capsule of the present invention starts to be limited to 200 ℃ on temperature (Ts) preferred.When above-mentioned foaming starts temperature over 200 ℃, particularly, the in the situation that of injection forming, expansion ratio can not improve sometimes.Above-mentioned foaming starts to be limited under temperature preferred 130 ℃, is limited to 180 ℃ on preferred.
The volume average particle size of thermal expansivity micro-capsule of the present invention is not particularly limited, and is limited to 10 μ m under preferred, is limited to 50 μ m on preferred.When above-mentioned volume average particle size is less than 10 μ m, for example, the in the situation that of thermal expansivity micro-capsule being coordinated in matrix resin and be shaped, the bubble of resulting foam molding is too small, and lightweight sometimes becomes insufficient.When above-mentioned volume average particle size surpasses 50 μ m, for example, thermal expansivity micro-capsule is coordinated in matrix resin and be shaped in the situation that, the bubble of resulting foam molding becomes excessive, sometimes at aspects such as intensity, becomes problem.Under above-mentioned volume average particle size preferred, be limited to 15 μ m, be limited to 40 μ m on preferred.
The method of thermal expansivity micro-capsule of the present invention manufacture is not particularly limited, and for example, can be listed below method etc.: by being prepared the operation of aqueous dispersion medium; The operation that makes oiliness mixed solution disperse in this aqueous dispersion medium, wherein, described oiliness mixed solution contains: contain nitrile monomer and have the monomer composition of the monomer of carboxyl, have more than 2 with the functional group of carboxyl reaction and do not have thermosetting resin and the volatile expanding agent of free-radical polymerised two keys in 1 molecule; And the operation that makes described monomer composition polymerization, thus, obtain following thermal expansivity micro-capsule: in comprising the shell that makes polymkeric substance that the monomer composition of the monomer that contains nitrile monomer and have carboxyl is polymerized and thermosetting resin, bag is as the volatile expanding agent of core agent.
Prepare in the operation of above-mentioned aqueous dispersion medium, for example, in polymerization container, add water, dispersion stabilizer and auxiliary stabilizer as required, thus, the aqueous dispersion medium that preparation contains dispersion stabilizer.In addition, as required, also can in above-mentioned aqueous dispersion medium, add nitrite alkali metal-salt, tin protochloride, tin chloride, potassium bichromate etc.
Above-mentioned dispersion stabilizer is not particularly limited, and for example, can enumerate: silicon-dioxide, calcium phosphate, magnesium hydroxide, aluminium hydroxide, ironic hydroxide, barium sulfate, calcium sulfate, sodium sulfate, caoxalate, calcium carbonate, calcium carbonate, barium carbonate, magnesiumcarbonate etc.
Above-mentioned auxiliary stabilizer is not particularly limited, for example, can enumerate: the condensation product of the condensation product of diethanolamine and aliphatic dicarboxylic acid, urea and formaldehyde, water-soluble nitrogenous compound, polyethylene oxide, Tetramethylammonium hydroxide, gelatin, methylcellulose gum, polyvinyl alcohol, dioctyl sulfosuccinic ester, Isosorbide Dinitrate, various emulsifying agents etc.
Above-mentioned water-soluble nitrogenous compound is not particularly limited, for example, can enumerate: Polyvinylpyrolidone (PVP), polymine, polyoxyethylene alkylamine, take poly-diakyl aminoalkyl group (methyl) acrylate that polydimethyl amino-ethyl methacrylic ester and polydimethyl amino-ethyl acrylate be representative, take poly-diakyl aminoalkyl group (methyl) acrylamide that polydimethyl aminopropyl acrylamide and polydimethyl aminopropyl Methacrylamide be representative, polyacrylamide, polycation acrylamide, polyamine sulfone, PAH etc.In these, be preferably Polyvinylpyrolidone (PVP).
The combination of above-mentioned dispersion stabilizer and above-mentioned auxiliary stabilizer is not particularly limited, for example, can enumerate: the combination of the combination of the combination of colloid silica and condensation product, colloid silica and water-soluble nitrogenous compound, magnesium hydroxide or calcium phosphate and emulsifying agent etc.In these, the preferably combination of colloid silica and condensation product, as this condensation product, be preferably the condensation product of diethanolamine and aliphatic dicarboxylic acid, be particularly preferably the condensation product of condensation product, diethanolamine and the methylene-succinic acid of diethanolamine and hexanodioic acid.
As above-mentioned dispersion stabilizer, use in the situation of colloid silica, the addition of colloid silica is not particularly limited, can suitably determine according to the particle diameter of the thermal expansivity micro-capsule as target, with respect to being limited to 1 weight part under whole monomer component 100 weight parts preferred, be limited to 20 weight parts on preferred, be limited to 2 weight parts under further preferred, be limited to 10 weight parts on further preferred.
In addition, as above-mentioned auxiliary stabilizer, use in the situation of above-mentioned condensation product or above-mentioned water-soluble nitrogenous compound, the addition of above-mentioned condensation product or water-soluble nitrogenous compound is not particularly limited, can suitably determine according to the particle diameter of the thermal expansivity micro-capsule as target, with respect to being limited to 0.05 weight part under whole monomer component 100 weight parts preferred, being limited to 2 weight parts on preferred.
In above-mentioned aqueous dispersion medium, except above-mentioned dispersion stabilizer and above-mentioned auxiliary stabilizer, can also add the inorganic salt such as sodium-chlor, sodium sulfate.By adding such inorganic salt, can access the thermal expansivity micro-capsule with more uniform particle shape.
The addition of above-mentioned inorganic salt is not particularly limited, and with respect on whole monomer component 100 weight parts preferred, is limited to 100 weight parts.
Above-mentioned aqueous dispersion medium, by above-mentioned dispersion stabilizer and above-mentioned auxiliary stabilizer are coordinated and prepared in deionized water, the pH of above-mentioned deionized water, can suitably determine according to the kind of used dispersion stabilizer and auxiliary stabilizer.For example, in the situation that using the silicon-dioxide such as colloid silica as above-mentioned dispersion stabilizer, as required, add the acid such as hydrochloric acid, by the pH regulator to 3 of system～4, in operation described later, under acidic conditions, carry out polymerization.In addition, as above-mentioned dispersion stabilizer, use in the situation of magnesium hydroxide or calcium phosphate, system is adjusted to alkalescence, under operation neutral and alkali condition described later, carry out polymerization.
When manufacturing thermal expansivity micro-capsule of the present invention, then, the operation that the oiliness mixed solution that carries out making in above-mentioned aqueous dispersion medium containing above-mentioned monomer composition, thermosetting resin and above-mentioned volatile expanding agent disperses.
In this operation, can in above-mentioned aqueous dispersion medium, add respectively above-mentioned monomer composition, thermosetting resin and above-mentioned volatile expanding agent, in this aqueous dispersion medium, prepare above-mentioned oiliness mixed solution, conventionally in advance the two is obtained by mixing after oiliness mixed solution, adds in above-mentioned aqueous dispersion medium.Now, in container, preparing above-mentioned oiliness mixed solution and above-mentioned aqueous dispersion medium separately in advance, when stirring in other container, mixing, thus, after can making above-mentioned oiliness mixed solution disperse in above-mentioned aqueous dispersion medium, add in polymerization container.
It should be noted that, for the monomer in above-mentioned monomer composition is carried out to polymerization, use polymerization starter, above-mentioned polymerization starter can add in advance in above-mentioned oiliness mixed solution, after also above-mentioned aqueous dispersion medium and above-mentioned oiliness mixed solution can being uniformly mixed in polymerization container, adds.
In the operation that the oiliness mixed solution that makes to contain above-mentioned monomer composition and above-mentioned volatile expanding agent in above-mentioned aqueous dispersion medium disperses, in above-mentioned aqueous dispersion medium, make above-mentioned oiliness mixed solution carry out emulsion dispersion with the particle diameter of regulation.
The method of above-mentioned emulsion dispersion is not particularly limited, and for example, can enumerate: the method for example, stirring by homogenizer (, special machine chemical industry company system) etc.; Method by silent oscillation diverting devices such as line mixer, component type silent oscillation decollators etc.It should be noted that, can in above-mentioned silent oscillation diverting device, supply with respectively above-mentioned aqueous dispersion medium and above-mentioned oiliness mixed solution, also can supply with the dispersion liquid after being pre-mixed, stirring.
When manufacturing thermal expansivity micro-capsule of the present invention, then, make the operation of above-mentioned monomer composition copolymerization.The method of above-mentioned copolymerization is not particularly limited, and for example, can enumerate: by heating the method that makes above-mentioned monomer composition polymerization.
Like this, in obtaining in comprising the shell that makes polymkeric substance that the monomer composition of the monomer that contains nitrile monomer and have carboxyl is polymerized and thermosetting resin, bag is as the thermal expansivity micro-capsule of the volatile expanding agent of core agent.Resulting thermal expansivity micro-capsule can be then through the operation of dewatering, carry out dry operation etc.
The purposes of thermal expansivity micro-capsule of the present invention is not particularly limited, for example, thermal expansivity micro-capsule of the present invention is coordinated in matrix resin, use the manufacturing process such as injection forming, extrusion molding to form, thus, can manufacture possess thermal insulation, the foam molding of disconnected hot, sound-proofing, sound absorbing, vibrationproof, lightweight etc.Thermal expansivity micro-capsule of the present invention, breaks and shrinks even if be at high temperature also difficult to produce, and can foam with high foamability, therefore, also is preferably applicable to have the foaming and molding of the operation at high temperature heating.
The masterbatch pellet that adds the matrix resins such as thermoplastic resin in thermal expansivity micro-capsule of the present invention, is used the manufacturing process such as injection forming to form, and the heating during by shaping makes above-mentioned thermal expansivity micro-capsule foaming, thus, can manufacture foam molding.Such masterbatch is also one of the present invention.
As above-mentioned thermoplastic resin, only otherwise hinder object of the present invention, there is no particular limitation, for example, can enumerate: the general thermoplastic resins such as polyvinyl chloride, polystyrene, polypropylene, poly(propylene oxide), polyethylene; The engineering plastics such as polybutylene terephthalate, nylon, polycarbonate, polyethylene terephthalate.In addition, can use the thermoplastic elastomers such as vinyl, polyvinyl chloride-base, olefines, amino formate, ester class, also these resin combination can be used.
In above-mentioned thermoplastic resin 100 weight parts, the addition of thermal expansivity micro-capsule is 0.5～20 weight part, and preferably 1～10 weight part is applicable to.In addition, also can and use with the chemical foaming agent such as sodium bicarbonate (bicarb of soda) or ADCA (azo).
As the method for manufacturing above-mentioned masterbatch pellet, there is no particular limitation, for example; can be listed below method etc.: use equidirectional twin screw extruder etc., the starting material such as the matrix resins such as thermoplastic resin, various additives are carried out in advance mixing, then; be heated to specified temperature; add after the whipping agents such as thermal expansion micro-capsule of the present invention, further carry out mixingly, use tablets press; the mixing thing obtaining is thus cut into desired size; thus, form particle shape, obtain masterbatch pellet.
In addition, with step mixing roll by the starting material such as the matrix resins such as thermoplastic resin and thermal expansivity micro-capsule carry out mixing after, by tablets press, carry out granulation, thus, can manufacture the masterbatch pellet of particle shape.
As above-mentioned mixing roll, so long as can carry out mixing mixing roll in the situation that not destroying thermal expansivity micro-capsule, be not particularly limited, for example, can enumerate: pressurization kneader, Banbury mixer etc.
Invention effect
According to the present invention, can provide maintain high foamability and be at high temperature difficult to produce the thermal expansivity micro-capsule break and to shrink, the manufacture method of the foaminess thermoplastic resin masterbatch, foam molding and this thermal expansivity micro-capsule that use this thermal expansivity micro-capsule.
Embodiment
Below, enumerate embodiment and in further detail mode of the present invention is described, but the present invention is not only defined in these embodiment.
(embodiment 1～25, comparative example 1～8)
In polymerization container, drop into water 250 weight parts, as the colloid silica of dispersion stabilizer (rising sun electrification company system 20 % by weight) 25 weight parts and Polyvinylpyrolidone (PVP) (BASF AG's system) 0.8 weight part and 1N hydrochloric acid 1.8 weight parts, prepare aqueous dispersion medium.
Then, the oily mixture that the monomer of proportioning as shown in Table 1, thermosetting resin, linking agent, polymerization starter, volatile expanding agent are formed adds in aqueous dispersion medium, makes its suspendible, prepares dispersion liquid.Resulting dispersion liquid is uniformly mixed with homogenizer, in the pressure polymerization pot after nitrogen replacement, feeds intake, pressurization (0.5MPa) limit, limit at 60 ℃, react 6 hours, at 80 ℃, react 5 hours, thus, obtain reaction product.For resulting reaction product, after repeatedly filtering and washing, dry, thus, obtain thermal expansivity micro-capsule.
It should be noted that, as thermosetting resin, use
Bisphenol A type epoxy resin (エ ピ コ mono-ト 828US: the number of japan epoxy resin company system, free-radical polymerised pair of key: 0, with the number of the functional group of carboxyl reaction: 2),
Amino-benzene phenol-type epoxy resin (jER630: the number of japan epoxy resin company system, free-radical polymerised pair of key: 0, with the number of the functional group of carboxyl reaction: 3),
Hydrogenation bisphenol A type epoxy resin (YX8000: the number of japan epoxy resin company system, free-radical polymerised pair of key: 0, with the number of the functional group of carboxyl reaction: 2),
Hydrogenation glycidyl group amine type epoxy resin (TETRAD-C: the number of chemistry company of Mitsubishi system, free-radical polymerised pair of key: 0, with the number of the functional group of carboxyl reaction: 2),
Glycidyl group amine type epoxy resin (TETRAD-X: the number of chemistry company of Mitsubishi system, free-radical polymerised pair of key: 0, with the number of the functional group of carboxyl reaction: 4),
Phenolic varnish type resol (PR-50731: the number of Sumitomo ベ mono-Network ラィ ト company system, free-radical polymerised pair of key: 0, with the number of the functional group of carboxyl reaction: n (n >=2)),
Sorbitol Powder poly epihydric alcohol base ether (Na ガ セ ケ ムテツク ス company system), the number of free-radical polymerised pair of key デ Na コ mono-Le EX-622:: 0, with the number of the functional group of carboxyl reaction: 4),
As linking agent, use
Viscoat 295 (number of free-radical polymerised pair of key: 3, with the number of the functional group of carboxyl reaction: 0),
Glycidyl methacrylate (number of free-radical polymerised pair of key: 1, with the number of the functional group of carboxyl reaction: 1),
N hydroxymethyl acrylamide (the number of free-radical polymerised pair of key: 1, with the number of the functional group of carboxyl reaction: 1).
(evaluation)
Thermal expansivity micro-capsule about obtaining in the thermosetting resin, linking agent and the embodiment that use in embodiment, comparative example, comparative example, carries out following evaluation.Show the result in table 1～3.
(1) gel percentage
Use the Antoine equation shown in following, the temperature (T1.5) when the temperature (T1.0) when the vapour pressure that calculates the core agent of using in embodiment and comparative example reaches 1.0MPa and vapour pressure reach 1.5MPa.For the mixture of iso-pentane and octane-iso, by ratio of mixture, calculate T1.0 and T1.5.
log
10P＝A-(B/(T+C))
In formula, P is that vapour pressure, T are that temperature, A, B and C are Antoine constant.It should be noted that, the Antoine constant of iso-pentane and octane-iso is as follows.
Iso-pentane: A=6.78967, B=1020.12, C=233.97
Octane-iso: A=7.372, B=1578.81, C=230.7
Then, the thermosetting resin using in embodiment and comparative example or linking agent 0.5g are mixed in aluminium cup with citric acid 0.15g, with hot plate (CHPS-170DR, ASONE company system) heating 1 minute.Then, sample after heating is dropped into N, in dinethylformamide 100g, with 75 ℃ * 12 hours, make above after its swelling, with stainless steel sift (perforate: 200 order/inches) filter swelling body, after carrying out being dried for 170 ℃ * 2 hours together with stainless steel sift, working sample weight (swelling body dry weight), measures gel percentage by following formula.It should be noted that, about gel percentage, measure the gel percentage under T1.0 and T1.5, by following benchmark, evaluate.
By meet " the gel percentage under T1.0 is less than 5% " and " the gel percentage under T1.5 is more than 5% " the two situation be set as " ◎ ",
The situation that does not meet " the gel percentage under T1.0 is less than 5% " and " the gel percentage under T1.5 is more than 5% " the two or any one is set as to " zero ".
Gel percentage (%)=(swelling body dry weight/0.615
※) * 100
※ 0.615 (g)=0.5 (g) [weight of thermosetting resin]+0.15 (g) [weight of citric acid])
(2) expansion ratio
Use foamable microscope equipment (ジ ヤ パ Application ハイテツ Network company system), the expansion ratio while measuring maximum foaming.
Expansion ratio when maximum is foamed is less than the average evaluation of 3 times for " * ", by 3 times above and to be less than the average evaluation of 5 times be " zero ", by 5 times of above average evaluations, be " ◎ ".
(3) thermotolerance
Use foamable microscope equipment (ジ ヤ パ Application ハイテツ Network company system), the expansion ratio at measuring 250 ℃.Expansion ratio at 250 ℃ is less than to the average evaluation of 2 times for " * ", by 2 times above and to be less than the average evaluation of 3 times be " zero ", by 3 times of above average evaluations, be " ◎ ".
(4) weather resistance
In the situation that using foamable microscope equipment (ジ ヤ パ Application ハイテツ Network company system) to measure expansion ratio, measuring expansion ratio is 2 times of above temperature amplitudes (Δ T).
Δ T is less than to the average evaluation of 50 ℃ for " * ", by 50 ℃ above and to be less than the average evaluation of 65 ℃ be " zero ", by 65 ℃ of above average evaluations, be " ◎ ".
Table 1
Table 2
Table 3
(embodiment 26)
(manufacture of foaminess thermoplastic resin masterbatch)
Using powder shaped and granular Low Density Polyethylene 100 weight parts with carry out mixingly with Banbury mixer as stearic acid 10 weight parts of lubricant, while reaching approximately 100 ℃, add thermal expansivity micro-capsule 100 weight parts that obtain in embodiment 1.Afterwards, further carry out 30 seconds mixing, when extruding, carry out granulating, obtain masterbatch pellet.
(manufacture of foam molding)
Resulting masterbatch pellet 4 weight parts, TPE (Mitsubishi Chemical Ind's system, ラ バ ロ Application MJ4300C) 100 weight parts and pigment (carbon black/PE) 3 weight parts are mixed, resulting composite grain is supplied with to possessing in the hopper of screw type injection machine of store battery, carry out melting mixing, carry out injection forming, obtain tabular foam molding.It should be noted that, molding condition is: cylinder temperature: 230 ℃, die temperature: 50 ℃.
(embodiment 27)
In (manufacture of foam molding), except using following method, operation, obtains foam molding similarly to Example 26.
(manufacture of foam molding)
Resulting masterbatch pellet 2.5 weight parts, thermoplastic elastomer (Ha イ ト レ Le 3078, デユポ Application company system) 100 weight parts, pigment (カ ラ mono-MB, Tokyo ink company system) 3 weight parts are mixed, resulting composite grain is supplied with in the hopper of extrusion shaper, carry out melting mixing, carry out extrusion molding, obtain tabular foam molding.It should be noted that, extrusion condition is die temperature: 190 ℃.
(comparative example 9)
As thermal expansivity micro-capsule, use the thermal expansivity micro-capsule obtaining in comparative example 1, in addition, operation, obtains masterbatch pellet and foam molding similarly to Example 26.
(comparative example 10)
In (manufacture of foam molding), use method similarly to Example 27, in addition, operate equally with comparative example 7, obtain foam molding.
(comparative example 11)
As thermal expansivity micro-capsule, use the thermal expansivity micro-capsule obtaining in comparative example 2, in addition, operation, obtains masterbatch pellet and foam molding similarly to Example 26.
(comparative example 12)
In (manufacture of foam molding), use method similarly to Example 27, in addition, operate equally with comparative example 9, obtain foam molding.
(evaluation)
(5) expansion ratio
Measure after the proportion (D1) of resulting foam molding and the proportion (D0) of base material, with these, than (D0/D1), calculate, obtain expansion ratio.It should be noted that, use electronic hydrometer (ミ ラ mono-ヅ ユ trade Zhu Shihui company system, ED-120T), measure proportion.
The average evaluation that expansion ratio is less than to 2 times is " * ", by 2 times of above average evaluations, is " zero ".
(6) Du's sieve hardness (sense of touch)
The method of use based on JIS K 6253, is used Du's sieve A type hardness tester meter (polymer gauge Zhu Shihui company system, Asker durometer Model.A), measures Du sieve's hardness of resulting foam molding.
Du's sieve hardness being surpassed to 50 average evaluation is " * ", by the average evaluation below 50, is " zero ".
(7) quiet rigidity (quiet Gang degree)
On the surface of resulting foam molding, place pressure head (stainless steel,
cylindric), by its height setting, be 0.Then, measure the displacement that increases the weight of the moment point of 60 seconds (S1) that pressure head is applied to 91.5N, afterwards, measure the displacement that increases the weight of the moment point of 60 seconds (S2) that applies 320N, according to following calculating formula, calculate quiet rigidity.
Quiet rigidity=(320-91.5)/(S2-S1) [N/mm]
It should be noted that, in mensuration, use static materials trier (Dao Feng manufacturing company system, EZGraph).
Quiet rigidity being surpassed to 200 average evaluation is " * ", by the average evaluation below 200, is " zero ".
(8) dynamic stiffness and the output ratio of Q-switching to free running
On the surface of resulting foam molding, place pressure head (stainless steel,
cylindric), by its height setting, be 0.When pressure head is applied the upper limit and sets the circulation of 320N, lower limit set 91.5N and increase the weight of 1000 times, measure from being circulated to the mean value of the following project of 1000 circulations for 900 times.
Increasing the weight of under the upper limit increases the weight of (FU) and displacement (SU)
Increasing the weight of under lower limit increases the weight of (FD) and displacement (SD)
Then,, according to following calculating formula, calculate dynamic stiffness.
Dynamic stiffness=(FU-FD)/(SU-SD) [N/mm]
It should be noted that, in mensuration, use Tensilon universal testing machine (エ mono-ア Application De デ イYi company system, UTA-500).
In addition, by resulting " dynamic stiffness " and " quiet rigidity ", according to following calculating formula, calculate the output ratio of Q-switching to free running.
The output ratio of Q-switching to free running=dynamic stiffness/quiet rigidity [doubly]
The average evaluation that the output ratio of Q-switching to free running is surpassed to 1.5 times is " * ", by 1.5 times of following average evaluations, is " zero ".
Table 4
The possibility of utilizing in industry
According to the present invention, can provide maintain high foamability and be at high temperature difficult to produce the thermal expansivity micro-capsule break and to shrink, the manufacture method of the foaminess thermoplastic resin masterbatch, foam molding and this thermal expansivity micro-capsule that use this thermal expansivity micro-capsule.
Claims (7)
1. a thermal expansivity micro-capsule, is characterized in that, is wrapped in the shell consisting of polymkeric substance in the volatile expanding agent as core agent,
Described shell contains: polymkeric substance and thermosetting resin that the monomer composition of the monomer that contains nitrile monomer and have carboxyl is polymerized,
With respect to whole monomer component 100 weight parts, described monomer composition contains monomer 1～50 weight part with carboxyl,
Described thermosetting resin has more than 2 the functional group with carboxyl reaction in 1 molecule, and does not have free-radical polymerised two keys.
2. thermal expansivity micro-capsule according to claim 1, is characterized in that, with the functional group of carboxyl reaction be epoxy group(ing).
3. thermal expansivity micro-capsule according to claim 1 and 2, it is characterized in that, for thermosetting resin, temperature when the vapour pressure of core agent is reached to 1.0MPa is made as T1.0, the temperature when vapour pressure of described core agent is reached to 1.5MPa is while being made as T1.5, gel percentage under T1.0 is less than 5%, and the gel percentage under T1.5 is more than 5%.
4. according to the thermal expansivity micro-capsule described in claim 1,2 or 3, it is characterized in that, the content of thermosetting resin is 0.01～30 % by weight with respect to the polyalcohol integral that forms shell.
5. a foaminess thermoplastic resin masterbatch, is characterized in that, contains thermal expansivity micro-capsule and thermoplastic resin described in claim 1,2,3 or 4.
6. a foam molding, is characterized in that, is that right to use requires thermal expansivity micro-capsule or foaminess thermoplastic resin masterbatch claimed in claim 5 described in 1,2,3 or 4 to form.
7. a manufacture method for thermal expansivity micro-capsule, it for the manufacture of the thermal expansivity micro-capsule described in claim 1,2,3 or 4, is characterized in that, comprising:
The operation of preparing aqueous dispersion medium;
The operation that makes oiliness mixed solution disperse in this aqueous dispersion medium, wherein, described oiliness mixed solution contains: contain nitrile monomer and have the monomer composition of the monomer of carboxyl, have more than 2 with the functional group of carboxyl reaction and do not have thermosetting resin and the volatile expanding agent of free-radical polymerised two keys in 1 molecule; And
Make the operation of described monomer composition polymerization.
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| PCT/JP2011/055945 WO2011118437A1 (en) | 2010-03-26 | 2011-03-14 | Thermally expandable microcapsule |
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| CN105026511B (en) * | 2013-09-26 | 2017-03-08 | 积水化学工业株式会社 | Thermal expansivity microcapsule |
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| EP3892654A4 (en) * | 2019-02-01 | 2022-08-17 | Sekisui Chemical Co., Ltd. | Thermally expandable microcapsules and foam molding composition |
| US20220325061A1 (en) * | 2019-09-27 | 2022-10-13 | Sekisui Chemical Co., Ltd. | Foam and method for manufacturing foam |
| TWI821428B (en) * | 2019-10-04 | 2023-11-11 | 豐泰企業股份有限公司 | Three-dimensional printing thermal expansion structure manufacturing method |
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| WO1999043758A1 (en) * | 1998-02-24 | 1999-09-02 | Matsumoto Yushi-Seiyaku Co., Ltd. | Heat-expandable microcapsules, process for producing the same, and method of utilizing the same |
| JP2005029607A (en) * | 2003-07-08 | 2005-02-03 | Sanyo Chem Ind Ltd | Thermally expansible microcapsule |
| JP4567980B2 (en) | 2004-01-26 | 2010-10-27 | 三洋化成工業株式会社 | Thermally expandable microcapsules and hollow resin particles |
| JP2005213379A (en) * | 2004-01-29 | 2005-08-11 | Sanyo Chem Ind Ltd | Thermally expandable microcapsule |
| JP2005232274A (en) | 2004-02-18 | 2005-09-02 | Sekisui Chem Co Ltd | Thermally expandable microcapsule of high heat resistance and method for producing the same |
| JP5255200B2 (en) * | 2005-12-21 | 2013-08-07 | 積水化学工業株式会社 | Thermally expandable microcapsules and foamed molded articles |
| JP2009221429A (en) * | 2008-03-18 | 2009-10-01 | Sekisui Chem Co Ltd | Thermally expandable microcapsule and foamed molded body |
| WO2012032991A1 (en) * | 2010-09-06 | 2012-03-15 | 積水化学工業株式会社 | Foamable resin composition and foam molded body |
| TWI554559B (en) * | 2010-12-28 | 2016-10-21 | Sekisui Chemical Co Ltd | And a resin composition for foam molding |
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| CN102812101A (en) | 2012-12-05 |
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